Metal cation crosslinked, partially reduced graphene oxide membranes with enhanced stability for high salinity, produced water treatment by pervaporative separation.

Graphene oxide (GO)-based membranes hold significant promise for applications ranging from energy storage to protective coatings, to saline water and produced water treatment, owing to their chemical stability and unique barrier properties achieving a high selectivity for water permeation. However, unmodified GO membranes are not stable when submerged in liquid water, creating challenges with their commercial utilization in aqueous filtration and pervaporation applications. To mitigate this, we develop an approach to modify GO membranes through a combination of low temperature thermal reduction and metal cation crosslinking. We demonstrate that Zn2+-rGO and Fe3+-rGO membranes had the highest permeation flux of 8.3 ±1.5 L m-2 h-1 and 
7.0 ± 0.4 L m-2 h-1, for saline water separation, respectively, when thermally reduced after metal cross-linking; These membranes maintained a high flux of 7.5 ± 0.7 L m-2 h-1, and 5.5 ± 0.3 L m-2 h-1 for produced water separation, respectively. All the membranes had a salt rejection higher than 99%. Fe3+ crosslinked membranes presented the highest organic solute rejections for produced water of 69%. Moreover, long term pervaporation testing was done for the Zn2+-rGO membrane for 12 hours, and only a minor drop of 6% in permeation flux in permeation flux was observed, while Zn2+-GO had a drop of 24%. Both modifiers significantly enhanced the stability with Fe3+-rGO membranes display the highest mechanical abrasion resistance of 95% compared to non-reduced and non-crosslinked GO. Improved stability for all samples also led to higher selectivity to water over organic contaminants and only slightly reduced water flux across the membrane.&#xD.